JP6506184B2 - Photosensitive resin composition, method of producing cured product, cured film, display device, and touch panel - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured product, a cured film, a display device, and a touch panel.

BACKGROUND Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. Also, in recent years, with the spread of smartphones and tablet terminals, electrostatic capacitive touch panels have attracted attention. The sensor substrate of the capacitive touch panel includes a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc.) on glass or film, and It is common to have a wiring in which the laminates and alloys thereof are patterned, and to have an insulating film, an ITO, and a protective film for protecting metal at intersections of the wirings.
As a conventional photosensitive resin composition, what was described in patent document 1 is known.

JP, 2013-152353, A

  The problem to be solved by the present invention is a photosensitive resin composition excellent in developability and excellent in hardness of the obtained cured product and corrosion resistance to metal wiring, and curing using the photosensitive resin composition It is providing a manufacturing method of a thing, a cured film which hardens the above-mentioned photosensitive resin composition, and a display and a touch panel using the above-mentioned cured film.

The above problems of the present invention are solved by the means described in <1>, <10>, <12> or <14> below. It describes below with <2>-<9>, <11> and <13> which are preferable embodiment.
<1> A polymer component satisfying at least one of the following I and II, a quinonediazide compound, a solvent, a triazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound and a benzoimidazole compound A photosensitive resin composition comprising at least one heterocyclic compound, and a maleimide compound,
I: Polymer component including a structural unit having a carboxy group and / or a salt thereof and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof And a polymer component including a polymer having a constituent unit having an epoxy group and / or an oxetanyl group <2> The compound in which the above-mentioned heterocyclic compound is represented by any one of the following formulas D1 to D12 The photosensitive resin composition according to <1>,

In formulas D1 to D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group. , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4.

  The photosensitive resin composition as described in <1> or <2> in which the <3> above-mentioned maleimide compound contains the compound represented by following formula E1,

In formula E1, R ^e1 each independently represents a single bond, an alkylene group, -SO _2- , -SO-, -S- or -O-, and R ^e2 each independently represents a halogen atom or an alkyl group. And m1 represent an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.

The photosensitive resin composition as described in any one of <1>-<3> which further contains a <4> silica particle,
The photosensitive resin composition as described in <4> whose average primary particle diameter of the <5> above-mentioned silica particle is 1-50 nm,
The photosensitive resin composition as described in <4> or <5> whose content of the said <6> above-mentioned silica particle is 5 mass% or more and less than 40 mass% with respect to the total solid of the photosensitive resin composition,
The photosensitive resin composition as described in <2> whose <7> above-mentioned heterocyclic compound is a compound represented by either the said Formula D1, Formula D2, and Formula D4-Formula D12,
The photosensitive resin composition as described in <7> whose <8> above-mentioned heterocyclic compound is a compound represented by either of said Formula D4-Formula D12,
<9> A method of producing a cured product, comprising at least steps a to d in this order,
Step a: Coating step of applying the photosensitive resin composition according to any one of <1> to <8> onto a substrate Step b: Solvent removal step of removing the solvent from the coated photosensitive resin composition Step c: Exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed by actinic radiation Step d: Heat treatment step of heat treating the exposed photosensitive resin composition <10> Step c, step d and <9>, the method of producing a cured product according to <9>, comprising
Step e: Developing step of developing the exposed photosensitive resin composition with an aqueous developing solution A cured film obtained by curing the photosensitive resin composition according to any one of <11><1> to <8> ,
The cured film as described in <11> which is <12> interlayer insulation film or overcoat film,
The display apparatus which has a cured film as described in <13><11> or <12>,
The touch panel which has a cured film as described in <14><11> or <12>.

  According to the present invention, a photosensitive resin composition excellent in developability and excellent in hardness of the obtained cured product and corrosion resistance to metal wiring, and a method of producing a cured product using the photosensitive resin composition A cured film formed by curing the photosensitive resin composition, and a display device and a touch panel using the cured film can be provided.

The structural conceptual diagram of an example of an organic electroluminescence display is shown. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarization film 4 is provided. FIG. 1 shows a conceptual diagram of an example of a liquid crystal display device. A schematic cross-sectional view of an active matrix substrate in a liquid crystal display device is shown, and it has a cured film 17 which is an interlayer insulating film. FIG. 1 shows a conceptual diagram of an example of a liquid crystal display device having a touch panel function. The structural conceptual diagram of another example of the liquid crystal display device which has a function of a touch panel is shown.

Hereinafter, the contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, when a numerical range is expressed as “to”, the numerical range means a range including the lower limit and the upper limit described before and after it. Moreover, the organic EL element in this invention means the thing of an organic electroluminescent element.
With regard to the notation of the compounds in the present specification, the non-description of substituted and unsubstituted in “group (group of atoms)” also includes a group having a substituent as well as an unsubstituted group. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Moreover, the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate | omitted the hydrogen atom.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acrylic” represents acrylic and methacrylic, and “(meth) acryloyl” represents acryloyl and methacryloyl.
Further, in the present invention, “a polymer component containing a polymer having a structural unit a1 having an acid group protected by an acid-degradable group” is also simply referred to as “component A” or the like.
Moreover, in the present invention, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
In the present invention, two or more combinations of preferred embodiments are more preferred embodiments.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises a polymer component satisfying at least one of the following I and II, a quinone diazide compound, a solvent, a triazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound and a benzo It is characterized in that it contains at least one heterocyclic compound selected from the group consisting of imidazole compounds, and a maleimide compound.
I: Polymer component including a structural unit having a carboxy group and / or a salt thereof and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof And a polymer component including a polymer having a structural unit having an epoxy group and / or an oxetanyl group

Although the detailed mechanism of the present invention is unknown, as a result of the present inventors' detailed investigations, the specific polymer component, the quinonediazide compound, the solvent, the specific heterocyclic compound, and the maleimide compound It was found that the photosensitive resin composition having excellent developability, excellent hardness of the obtained cured product, and excellent corrosion resistance to metal wiring can be obtained by the incorporation.
Hereinafter, each component of the photosensitive resin composition will be described in order.

<Polymer component satisfying at least one of I and II>
The photosensitive resin composition of the present invention contains a polymer component satisfying at least one of the following I and II.
I: Polymer component including a structural unit having a carboxy group and / or a salt thereof and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof And a polymer component containing a polymer having a constituent unit having an epoxy group and / or an oxetanyl group The polymer component as a whole comprises a carboxy group and / or a salt thereof, an epoxy group and / or an oxetanyl group By having a crosslinkable group of a group, curing reaction becomes possible.

It is preferable that the said polymer component is a polymer component which satisfy | fills said I.
Moreover, the photosensitive resin composition of this invention may contain polymers other than the polymer shown to said I and II further.

Each polymer in the polymer component is preferably an addition polymerization resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than structural units derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Moreover, "(meth) acrylic acid" shall mean "methacrylic acid and / or acrylic acid."

-A constituent unit having a carboxy group and / or a salt thereof-
The polymer component at least contains a polymer having a structural unit having a carboxy group and / or a salt thereof.
When the above-mentioned polymer component has a carboxy group and / or a salt thereof, it becomes easy to dissolve in an alkaline developing solution, and not only the developability becomes good, but also the sensitivity is excellent and the adhesion after development is also excellent.
The salt of the above carboxy group is a group having a salt structure by neutralizing the carboxy group, and the above salt is not particularly limited, but it is an alkali metal salt, an alkaline earth metal salt, an ammonium salt and an organic ammonium Salt can be preferably exemplified.
Among them, structural units having a carboxy group are preferred.

Specifically, as a constituent unit having a carboxy group, a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and both an ethylenically unsaturated group and a structure derived from an acid anhydride The structural unit which it has is mentioned.
As the unsaturated carboxylic acid used to form the above-mentioned constituent unit having a carboxy group, those listed below are used.
Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl Hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid and the like can be mentioned. Moreover, as unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. Also, the unsaturated polyvalent carboxylic acid may be its acid anhydride. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride and the like can be mentioned. The unsaturated polyvalent carboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester of polyvalent carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) and the like. Furthermore, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of its both terminal dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. Further, as unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, monoalkyl ester of maleic acid, monoalkyl ester of fumaric acid, 4-carboxystyrene, etc. can be used.

The structural unit having both the ethylenically unsaturated group and the structure derived from the acid anhydride is derived from the monomer obtained by reacting the acid anhydride with the hydroxyl group present in the structural unit having the ethylenically unsaturated group. The unit is preferably
As the above acid anhydrides, known ones can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride and the like. Among these, from the viewpoint of developability, phthalic anhydride, tetrahydrophthalic anhydride or succinic anhydride is preferred.
From the viewpoint of developability, the reaction ratio of the acid anhydride to the hydroxyl group is preferably 10 to 100 mol%, and more preferably 30 to 100 mol%.

  Among them, as a structural unit having a carboxy group and / or a salt thereof, a structural unit derived from methacrylic acid (a structural unit represented by the following formula a1-1) or a structural unit derived from acrylic acid (a formula a1-2 below) Structural unit), and more preferably a structural unit derived from methacrylic acid (a structural unit represented by the following formula a1-1).

In formulas a1-1 and a1-2, R ^a independently represents a hydrogen atom, an alkali metal cation, an alkaline earth metal cation, an ammonium ion, or an organic ammonium ion.
Among them, R ^a is preferably ^a hydrogen atom.

In one polymer, constituent units having a carboxy group and / or a salt thereof can be used singly or in combination of two or more.
The structural unit having a carboxy group and / or a salt thereof is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 45 mol%, based on the structural units of all polymer components. -40 mol% is particularly preferred, and 5-35 mol% is most preferred.
In the present invention, when the content of the “constituent unit” is defined by the molar ratio, the “constituent unit” is the same as the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by polymer reaction or the like. The same applies to the following.

-A constituent unit having an epoxy group and / or an oxetanyl group-
The polymer component at least contains a polymer having a structural unit having an epoxy group and / or an oxetanyl group.
The 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit a2-1 having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups. It may have one or more groups, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and an epoxy group It is more preferable to have a total of one or two oxetanyl groups and / or one more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha) -ethyl acrylate, glycidyl (alpha) -n-propyl acrylate are mentioned, for example Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epo Such compounds may be mentioned containing shea skeleton, the contents of which are incorporated herein.
As a specific example of the radically polymerizable monomer used in order to form the structural unit which has oxetanyl group, the (meth) acryl which has oxetanyl group as described in stage 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953, for example These include acid esters and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used to form the structural unit a2-1 having the epoxy group and / or the oxetanyl group include a monomer having a methacrylic acid ester structure, and an acrylic acid ester structure. It is preferably a monomer.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetan-3-yl) methyl acrylate, and (3-ethyl methacrylate) Oxetan-3-yl) methyl is preferably mentioned. These constituent units can be used singly or in combination of two or more.

  The following structural unit can be illustrated as a preferable specific example of the structural unit which has an epoxy group and / or oxetanyl group. R represents a hydrogen atom or a methyl group.

  The content of the structural unit having the epoxy group and / or the oxetanyl group in the polymer having the structural unit having the epoxy group and / or the oxetanyl group is preferably 5 to 90% by mole with respect to all the structural units of the polymer 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable.

-Other constitutional unit-
In the present invention, each polymer represented by the above I or II may have other structural units other than these in addition to the two structural units described above.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid arylester, unsaturated Dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds can be mentioned.
The monomer which forms another structural unit can be used individually by 1 type or in combination of 2 or more types.

  Specifically, other structural units are styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3 -Methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Examples of the structural unit include 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate and the like. In addition, the compound as described in stage 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 can be mentioned.

  In addition, as other structural units, structural units derived from styrenes or monomers having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical properties. Specifically, styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate and the like can be mentioned.

  60 mol% or less is preferable with respect to all the structural units of a polymer, and, as for content of the said other structural units among all the structural units which comprise the said polymer, 50 mol% or less is more preferable, and 40 mol% or less More preferable. The lower limit may be 0 mol%, but is preferably 1 mol% or more, and more preferably 5 mol% or more. The various characteristics of the cured film obtained from the photosensitive resin composition become favorable in it being in the range of said numerical value.

-Molecular weight of polymer-
The molecular weight of each polymer in the above polymer component is independently preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and further preferably 10,000 to 20,000 in terms of weight average molecular weight in terms of polystyrene. Is more preferred. Various characteristics are favorable in it being in the said range. 1.0-5.0 are preferable and, as for ratio (dispersion degree, Mw / Mn) of number average molecular weight Mn and weight average molecular weight Mw, 1.5-3.5 are more preferable.
The measurement of the weight average molecular weight and the number average molecular weight in the present invention is preferably performed by gel permeation chromatography (GPC). In the measurement by gel permeation chromatography in the present invention, HLC-8020GPC (manufactured by Tosoh Corp.) is used, TSK gel Super HZ M-H, TSK gel Super HZ 4000, TSK gel Super HZ 200 (manufactured by Tosoh Corp., 4.6 mm ID) as a column It is preferred to use THF (tetrahydrofuran) as an eluent, x 15 cm).

-Method of producing polymer-
In addition, various methods are known for the synthesis method of the above-mentioned polymer, but one example is a radically polymerizable monomer containing a radically polymerizable monomer used to form each structural unit The mixture can be synthesized by polymerizing the mixture in an organic solvent using a radical polymerization initiator. Moreover, it can also be synthesized by so-called polymer reaction.

The content of the polymer component in the photosensitive resin composition of the present invention is preferably 20 to 95% by mass, and 50 to 93% by mass, with respect to the total organic solid content of the photosensitive resin composition. It is more preferable that the ratio be 55 to 90% by mass. When the content is in this range, a curable organic film can be obtained.
The total solid content of the photosensitive resin composition refers to all the components excluding the organic solvent, and the total organic solid content of the photosensitive resin composition refers to the inorganic components such as silica particles described later and the organic solvent All components except for.

<Quinone diazide compound>
The photosensitive resin composition of the present invention contains a quinone diazide compound.
As the quinone diazide compound, a 1,2-quinone diazide compound which generates a carboxylic acid upon irradiation with an actinic ray can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazide sulfonic acid halide can be used. As specific examples of these compounds, for example, the description in paragraphs “0075” to “0078” of Japanese Patent Application Laid-Open No. 2012-088459 can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of a phenolic compound or alcoholic compound (mother core) with 1,2-naphthoquinone diazide sulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound It is possible to use 1,2-naphthoquinone diazide sulfonic acid halide corresponding to%, more preferably 50 to 70 mol%. The condensation reaction can be carried out by known methods.

  In addition, as a 1,2-quinonediazide compound, 1,2-naphthoquinonediazide sulfonic acid amides in which the ester bond of the above-exemplified mother nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2 -A naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably. Also, 4,4 '-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mole) and 1,2-naphthoquinonediazide-5-sulfone Condensates with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 A condensation product of 2, 3, 4, 4'-tetrahydroxybenzophenone (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. You may use.

These quinone diazide compounds can be used singly or in combination of two or more.
The content of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the total organic solid content in the photosensitive resin composition. 10 to 25 parts by mass is more preferable. By setting the compounding amount of the quinone diazide compound in the above range, the solubility difference between the irradiated portion and the unirradiated portion of the actinic ray in the alkaline aqueous solution to be a developer is large, the patterning performance becomes good, The solvent property is good.

<Solvent>
The photosensitive resin composition of the present invention contains a solvent as Component C.
The photosensitive resin composition of the present invention comprises the above polymer component and the quinone diazide compound which are essential components, and an optional component described later, using an organic solvent in which the polymer component and the quinone diazide compound are dissolved. It is preferable to prepare the photosensitive resin composition as a liquid in which the components of (1) are dissolved and / or dispersed.
As the solvent, known organic solvents can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol Monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols , Esters, ketones, amides, lactones etc. . As a specific example of these organic solvents, paragraph 0062 of JP-A-2009-098616 can be referred to.

  Preferred examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydrofulf Furyl alcohol is mentioned.

The boiling point of the solvent is preferably 100 ° C. to 300 ° C., and more preferably 120 ° C. to 250 ° C., from the viewpoint of coatability.
The solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferable to use solvents having different boiling points in combination.
The content of the solvent in the photosensitive resin composition of the present invention is 100 to 3,000 parts by mass with respect to 100 parts by mass of the total organic solid content of the photosensitive resin composition from the viewpoint of adjusting the viscosity suitable for coating. The content is preferably 200 to 2,000 parts by mass, more preferably 250 to 1,000 parts by mass.
The solid content concentration of the photosensitive resin composition of the present invention is preferably 3 to 50% by mass, and more preferably 10 to 40% by mass.

<At least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds>
The photosensitive resin composition of the present invention comprises at least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds (hereinafter referred to as “specific complex compounds”. (Also referred to as “cyclic compound”). The photosensitive resin composition of the present invention is excellent in developability by containing a specific polymer component, a quinonediazide compound, a specific heterocyclic compound and a maleimide compound, and the hardness of the obtained cured product and the corrosion inhibition to metal wiring are obtained. It is estimated that it is excellent in the property and also excellent in the transparency of the obtained cured product.

  The specific heterocyclic compound is not particularly limited as long as it is a compound having a triazole ring structure, a tetrazole ring structure, a thiadiazole ring structure, a triazine ring structure, a rhodanine ring structure, a thiazole ring structure and / or a benzimidazole ring structure. It is preferable that it is a compound represented by either of Formula D1-Formula D12.

In formulas D1 to D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group. , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4.

  In addition, the compound represented by said Formula D1-Formula D3 is a triazole compound, The compound represented by said Formula D4 is a tetrazole compound, The compound represented by said Formula D5-Formula D7 is a thiadiazole compound, The compound represented by Formula D8 is a triazine compound, the compound represented by Formula D9 is a rhodanine compound, the compound represented by Formula D10 is a benzothiazole compound, and is represented by Formula D11 The compound is a benzimidazole compound, and the compound represented by the formula D12 is a thiazole compound.

R ¹ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ are each independently preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group, and hydrogen Particularly preferred is an atom.
R ⁵ is preferably a hydrogen atom, an alkyl group or an amino group, more preferably a hydrogen atom or an amino group.
R ^{2 to} R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, It is preferably an amino group, a mercapto group or an alkylthio group, and more preferably a hydrogen atom, an amino group, a mercapto group or an alkylthio group.
R ^{15 to} R ¹⁷ are preferably each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group or an alkylthio group, and more preferably an amino group or a heteroaryl group. Particularly preferred is an amino group or a pyridyl group.
From the viewpoint of ^synthesis, R 15 ^{to R 17} is preferably the same group.
R ¹⁸ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an amino group, a mercapto group or an alkylthio group, and hydrogen More preferably, it is an atom.
Each of R ⁶ , R ¹⁴ , R ²¹ and R ²³ independently represents an alkyl group, an aryl group, a heteroaryl group, an amino group, an alkylamino group, an arylamino group, a mercapto group, an alkylthio group, an arylthio group, a carboxy group, a hydroxy group It is preferably a group, an alkoxy group or an aryloxy group, and more preferably an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group, an alkylthio group, an arylthio group or a carboxy group.
Also, R ⁶ , R ¹⁴ , R ²¹ and R ²³ can substitute and bond a hydrogen atom at any position on the benzene ring in each of the above formulas.
R ¹⁹ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
n1 to n4 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

From the viewpoint of adhesion, the specific heterocyclic compound is preferably at least one heterocyclic compound selected from the group consisting of tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds, preferably tetrazole compounds. More preferably, it is at least one heterocyclic compound selected from the group consisting of a compound, a thiadiazole compound, a rhodanine compound, a thiazole compound and a benzimidazole compound, and at least one complex selected from the group consisting of a tetrazole compound and a thiadiazole compound More preferably, they are ring compounds. Further, the specific heterocyclic compound is preferably a compound represented by any one of the above formulas D1, D2 and D4 to D12 from the viewpoint of adhesion, and any one of the above formulas D4 to D12 It is more preferable that it is a compound represented, it is still more preferable that it is a compound represented by any one of Formula D4 to Formula D7 and Formula D9 to Formula D12, and it is represented by any one of Formula D4 to Formula D7. Particularly preferred are
The specific heterocyclic compound is preferably at least one heterocyclic compound selected from the group consisting of a thiadiazole compound and a triazine compound from the viewpoint of the corrosion resistance of metal wiring, and more preferably a thiadiazole compound. The specific heterocyclic compound is preferably a compound represented by any one of the above formulas D5 to D8 from the viewpoint of the corrosion resistance of metal wiring, and any one of the above formulas D5, D6 and D8. Is more preferably a compound represented by the formula D5, further preferably a compound represented by the formula D5 or a compound represented by the formula D6, and a compound represented by the formula D6 Particularly preferred.

Specifically as a specific heterocyclic compound, the compound shown below can be illustrated preferably.
The following compounds can be illustrated as a triazole compound.

  The following compounds can be illustrated as a tetrazole compound.

  The following compounds can be illustrated as a thiadiazole compound.

  The following compounds can be illustrated as a triazine compound.

  The following compounds can be illustrated as a rhodanine compound.

  The following compounds can be illustrated as a thiazole compound and a benzimidazole compound.

The specific heterocyclic compound may be contained singly or in combination of two or more.
The content of the specific heterocyclic compound in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the total organic solid content of the photosensitive resin composition. And 0.2 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass. It is excellent by the hardness of the hardened | cured material obtained as it is the said range, the corrosion prevention property to metal wiring, and excellent in the transparency of the hardened | cured material obtained.

<Maleimide compound>
The photosensitive resin composition of the present invention contains a maleimide compound.
The maleimide compound is not particularly limited as long as it is a compound having one or more groups represented by the following formula E, but it is preferable to include a compound having two or more groups represented by the following formula E, It is more preferable to include a compound having two or more maleimide groups.
In the present invention, a compound having two or more groups represented by the following formula E is a maleimide compound and is not included in the compound having two or more ethylenic unsaturated bonds.

In formula E, Y ¹ is —CH = CH—, —C (CH ₃ ) = CH—, —C (= CH ₂ ) —CH ₂ — or —C (CH ₃ ) = C (CH ₃ ) — And the dashed line portion indicates the bonding position with another structure.

Y ¹ is preferably —CH = CH—, —C (CH ₃ ) = CH— or —C (= CH ₂ ) —CH ₂ —, —CH = CH— or —C ( It is more preferable that CH ₃ ) = CH-, and it is particularly preferable that -CH = CH-.
The number of groups represented by Formula E in the maleimide compound is preferably 1 to 20, more preferably 1 to 10, still more preferably 2 to 8, and 2 Particularly preferred.
Further, from the viewpoint of the stability of the compound and the composition, in the above-mentioned maleimide compound, it is preferable that the nitrogen atom of the group represented by the above-mentioned formula E is directly bonded to the aromatic ring.
The maleimide compound preferably contains a compound having two groups represented by the following formula E, that is, a bismaleimide compound, from the viewpoint of hardness and corrosion prevention, and includes a compound represented by the following formula E1. Is more preferred.

In formula E1, R ^e1 each independently represents a single bond, an alkylene group, -SO _2- , -SO-, -S- or -O-, and R ^e2 each independently represents a halogen atom or an alkyl group. And m1 represent an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.

R ^e1 is preferably independently a single bond, an alkylene group having 1 to 8 carbon atoms, or -O-, and more preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or -O- More preferably, it is a single bond, a methylene group, a dimethylmethylene group (2,2-propylene group) or -O-.
Each R ^e2 is preferably independently an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably a methyl group or an ethyl group.
In addition, R ^e1 and R ^e2 can substitute and bond a hydrogen atom at any position on the benzene ring in the above-mentioned formula E1.
Further, R ^e1 is preferably bonded to the maleimide group or a group having a maleimide group at the p-position on the benzene ring in the above-mentioned formula E1.
m1 is preferably an integer of 1 to 5, more preferably an integer of 2 to 5, and still more preferably an integer of 3 to 5.
m2 is preferably independently an integer of 0 to 2;

  Specifically as said maleimide compound, the following compound can be mentioned preferably.

Moreover, the following bismaleimide compounds are also specifically mentioned as said maleimide compound.
1,6-Bismaleimide-2,4,4-trimethylhexane, N, N'-decamethylene bismaleimide, N, N'-octamethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N '-Trimethylene bismaleimide, bis [(2,5-dioxo-2,5-dihydropyrrol-1-yl) methyl] bicyclo [2.2.1] heptane, 4,4'-diphenylether bismaleimide, 4, 4'-diphenylsulfone bismaleimide, 4,4'-diphenyl sulfide bismaleimide, 3,3'-dimethyl-4,4'-diphenylmethane bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3 -Bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, 3,3 ', 5,5'- Tramethyl-4,4′-diphenylmethane bismaleimide, 3,3′-diethyl-4,4′-diphenylmethane bismaleimide, 3,3′-di-n-butyl-4,4′-diphenylmethane bismaleimide, 3,3 ', 5,5'-tetraethyl-4,4'-diphenylmethane bismaleimide etc.

The maleimide compound may be contained singly or in combination of two or more.
Although the content of the maleimide compound in the photosensitive resin composition of the present invention is not particularly limited, it is preferably 0.1 to 20% by mass with respect to the total organic solid content of the photosensitive resin composition, and 0 The content is more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass, and particularly preferably 3 to 8% by mass. It is excellent by the adhesiveness of the hardened | cured material obtained as it is the said range, and the corrosion prevention property to metal wiring.

<Silica particles>
The photosensitive resin composition of the present invention preferably contains silica particles. By containing the silica particles, the hardness of the obtained cured product becomes excellent.
Moreover, as a result of the inventors' investigations in detail, when the inventors contained silica particles, the inventors found that the corrosion to the metal wiring was less likely to progress, but the photosensitive resin composition of the present invention The present inventors have found that, by containing the above-mentioned specific heterocyclic compound and the above-mentioned maleimide compound, even if it contains silica particles, it is excellent in the corrosion resistance to metal wiring.
1-200 nm is preferable, as for the average primary particle diameter of the silica particle used by this invention, 1-100 nm is more preferable, 1-50 nm is still more preferable, 1-30 nm is especially preferable. The average primary particle size refers to an arithmetic mean of particle sizes of 200 arbitrary particles measured by an electron microscope. When the shape of the particles is not spherical, the maximum diameter of the outer diameter is taken as the particle diameter of the particles.
From the viewpoint of the hardness of the cured product, the porosity of the silica particles is preferably less than 10%, more preferably less than 3%, and particularly preferably no voids. The porosity of the particles is an arithmetic mean of 200 area ratios of void portions of the cross-sectional image by the electron microscope to the whole particles.

The silica particles are not particularly limited as long as they are particles of inorganic oxide containing silicon dioxide, and particles containing silicon dioxide or its hydrate as a main component (preferably 80% by mass or more) are preferable. The particles may contain an aluminate as a minor component (e.g. less than 5% by weight). As the aluminate which may be contained as a minor component, sodium aluminate, potassium aluminate and the like can be mentioned.
The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethyl ammonium hydroxide. Colloidal silica is illustrated as an example of such a silica.
There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. These may be used alone or in combination of two or more.
In the present invention, the particles can also be used as a dispersion prepared by mixing and dispersing in a suitable dispersing agent and solvent using a mixing apparatus such as a ball mill and a rod mill. In addition, when introduce | transducing a silica particle to the photosensitive resin composition of this invention using colloidal silica, it does not mean that colloidal silica exists in a colloid state also in a composition.

The silica particles may contain only one type, or two or more types.
The content of the silica particles is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, based on the total solid content of the photosensitive resin composition, from the viewpoint of corrosion prevention and hardness. . Moreover, 80 mass% or less is preferable, 60 mass% or less is more preferable, 50 mass% or less is still more preferable, and less than 40 mass% is especially preferable.

<Adhesive promoter>
The photosensitive resin composition of the present invention preferably contains an adhesion promoter.
Although a well-known adhesion promoter can be used as said adhesion promoter, An alkoxysilane compound is mentioned preferably. When an alkoxysilane compound is used, the adhesion between the film formed of the photosensitive resin composition of the present invention and the substrate can be improved.
The alkoxysilane compound is not particularly limited as long as it is a compound having at least one group in which an alkoxy group is directly bonded to a silicon atom, but a compound having a dialkoxysilyl group and / or a trialkoxysilyl group The compound is preferably a compound having a trialkoxysilyl group.
The alkoxysilane compound which can be used for the photosensitive resin composition of the present invention is a substrate, for example, a silicon compound such as silicon, silicon oxide, silicon nitride such as silicon nitride, metal such as gold, copper, molybdenum, titanium, aluminum It is preferable that it is a compound which improves adhesiveness with it. Specifically, known silane coupling agents are also effective. Silane coupling agents having an ethylenically unsaturated bond are preferred.
As a silane coupling agent, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, γ-methacryloxypropyl Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Be Among these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltrialkoxysilane are more preferable. These can be used singly or in combination of two or more.
As a commercial item, Shin-Etsu Chemical Co., Ltd. product and KBM-403 and KBM-5103 are illustrated.

The adhesion promoter may contain only one type, or two or more types.
The content of the adhesion promoter in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, based on the total organic solid content of the photosensitive resin composition. -15 mass% is further more preferable. When two or more adhesion promoters are contained, the total amount is preferably in the above range.

<Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. As surfactant, nonionic surfactant is preferable and fluorine surfactant is more preferable.
As surfactants which can be used in the present invention, for example, Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, which are commercially available products, can be used. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Co., Ltd. product), Asahi Guard AG7105, 7000, 950, 7600, Surfron S-112, S-113, S-131, S-131 -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, SC-106 (Asahi Glass Co., Ltd.), F-top EF 351, 352, 801, 802 (Mitsubishi Materials Electronics Kasei Co., Ltd.), Futargent 250 (Neos Co., Ltd.) . In addition to the above, KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (manufactured by DIC Corporation) And each series such as Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA) and the like.

  Moreover, as a surfactant, the compound as described in Unexamined-Japanese-Patent No. 2014-238438 Paragraph 0151-can also be mentioned as a preferable example.

The content of the surfactant in the photosensitive resin composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total organic solid content of the photosensitive resin composition, when blended. And 0.01 to 2.0 parts by mass are more preferable.
The surfactant may contain only one type, or two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to accelerate the decomposition thereof in combination with the quinone diazide compound.
The sensitizer absorbs an actinic ray to be in an electronically excited state. The sensitizer in the electronically excited state comes into contact with the quinone diazide compound to produce actions such as electron transfer, energy transfer, heat generation, and the like. As a result, the quinone diazide compound undergoes a chemical change to form an acid. Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength range of 350 nm to 450 nm.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg merocyanine, carbomerocyanine), rhodacyanines, oxonols, thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine) Dichloride, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls (for example For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3, 6) 7-Tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-non).

The sensitizer may be used alone or in combination of two or more.
The content of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the quinone diazide compound of the photosensitive resin composition. The content is more preferably 50 to 200 parts by mass.

<Crosslinking agent>
The photosensitive resin composition of the present invention may contain a crosslinking agent.
The crosslinking agent is preferably a crosslinking agent having a molecular weight of 1,000 or less.
As the above-mentioned crosslinking agent, any crosslinking agent can be used without limitation as long as the crosslinking reaction occurs by heat (however, the above polymer and the above alkoxysilyl compound are excluded). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a compound having two or more blocked isocyanate groups in the molecule (a compound having a protected isocyanato group), two in the molecule It is preferable to include at least one compound selected from the group consisting of a compound having the above alkoxymethyl group and a compound having at least one ethylenically unsaturated group, and two or more epoxy groups in the molecule It is more preferable that at least one selected from the group consisting of a compound having an oxetanyl group and two or more blocked isocyanate compounds in the molecule.

The content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0 to 30% by mass, and more preferably 1 to 20% by mass, with respect to the total organic solid content of the photosensitive resin composition. preferable.
The said crosslinking agent can also use multiple types together, and in that case, an addition amount is calculated by the total content which totaled all the crosslinking agents.
The crosslinking agent preferably used in the present invention will be described below.

-Compounds having two or more epoxy groups or oxetanyl groups in the molecule-
Examples of the compound having two or more epoxy groups or oxetanyl groups in the molecule include polyfunctional 3- and / or 4-membered cyclic ether compounds. That is, it is a compound having two or more epoxy groups and / or oxetanyl groups in one molecule. The molecular weight of this compound is preferably 1,000 or less. A small amount of a crosslinker having a molecular weight of more than 1,000 and less than 5,000, or a polymer crosslinker having a molecular weight of 5,000 or more may be used in combination with the low molecular weight crosslinker.

As a specific example of the compound which has a 2 or more epoxy group in a molecule | numerator, an aliphatic epoxy compound etc. can be mentioned.
These are commercially available. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-313, EX-314, EX-321. , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 , DLC-402 (all from Nagase ChemteX Co., Ltd.), Celoxide 2021 P, 2081, 3000, EHPE3. 50, Epolead GT400, Serubinasu B0134, B0177 (or, Ltd. Daicel), and the like.
These can be used singly or in combination of two or more.

  As a specific example of a compound which has a 2 or more oxetanyl group in a molecule | numerator, aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

  Moreover, it is preferable to use the compound which contains a 2 or more oxetanyl group in a molecule individually or in mixture with the compound which contains a 2 or more epoxy group in a molecule | numerator.

-Compounds having two or more blocked isocyanate groups in the molecule-
In the photosensitive resin composition of the present invention, as Component D, a compound having two or more block isocyanate groups in the molecule (simply referred to as "blocked isocyanate compound") can also be preferably adopted. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group in which an isocyanate group is chemically protected. The blocked isocyanate compound also uses a compound having a molecular weight of 1,000 or less as a crosslinking agent.
In addition, the block isocyanate group in this invention is group which can produce | generate an isocyanate group by heat, for example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can be illustrated preferably. Moreover, it is preferable that the said block isocyanate group is group which can produce | generate an isocyanate group by the heat | fever of 90 degreeC-250 degreeC.
The skeleton of the blocked isocyanate compound is not particularly limited, and may be any one having two isocyanate groups in one molecule, and it may be aliphatic, alicyclic or aromatic. The polyisocyanate may be, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2,4 '-Diethylether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylenebis (cyclohexylisocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditrilene-4,4'-diisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And the compound of the skeleton of the prepolymer type derived from these compounds can be used suitably. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

As a matrix structure of the said block isocyanate compound, a biuret type, an isocyanurate type, an adduct type, a bifunctional prepolymer type etc. can be mentioned.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, an imide compound and the like. be able to. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds are particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples thereof include acetoxy, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the above amine compound include primary amines and secondary amines, and may be any of aromatic amines, aliphatic amines and alicyclic amines, and aniline, diphenylamine, ethyleneimine, polyethyleneimine and the like are exemplified. it can.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compound include pyrazole, methyl pyrazole and dimethyl pyrazole.
Examples of the mercaptan compound include alkyl mercaptan and aryl mercaptan.

  Blocked isocyanate compounds that can be used in the present invention are commercially available products, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all, Nippon Polyurethane Industry Co., Ltd.) Made, Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all from Mitsui Chemical Co., Ltd.), Duranate 17B-60PX , 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (all, Asahi Kasei Chemicals Corporation) ), Death modules BL1100 and BL12 5 Preferably using MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Semidur BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd.), etc. Can.

-Compounds having two or more alkoxymethyl groups in the molecule-
Preferred examples of the compound having two or more alkoxymethyl groups in the molecule include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea. These are each obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril or methylolated urea into an alkoxymethyl group. The type of alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like, but from the viewpoint of the amount of outgassing, methoxy Methyl is particularly preferred.
Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine and alkoxymethylated glycoluril are mentioned as preferable compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.
The alkoxymethyl group-containing crosslinking agent also uses a compound having a molecular weight of 1,000 or less in the photosensitive resin composition.
Compounds having two or more alkoxymethyl groups in these molecules are commercially available products, and, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (above, Mitsui Cyanamid Co., Ltd.), Nikalac MX-750, -032, -706, -708, -708, -40, -31, -270, -280, -290, nicalac MS-11, nicalac MW-30HM, -100LM, -390 (all, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

-Compounds having at least one ethylenically unsaturated group-
As the compound having at least one ethylenically unsaturated group, (meth) acrylate compounds such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more functional (meth) acrylate and the like can be suitably used it can.
As monofunctional (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl -2-hydroxypropyl phthalate and the like.
Examples of difunctional (meth) acrylates include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples thereof include tetraethylene glycol di (meth) acrylate, bis phenoxy ethanol fluoro orange acrylate, bis phenoxy ethanol fluoro orange acrylate and the like.
Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
These compounds having at least one ethylenically unsaturated double bond may be used alone or in combination of two or more.
Moreover, when adding the compound which has at least 1 piece of ethylenically unsaturated double bond, it is preferable to add the below-mentioned heat radical generating agent.

<Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound.
The basic compound is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. The compound as described in stage 0204-0207 of Unexamined-Japanese-Patent No. 2011-221494 is mentioned as these specific examples.

Specifically, as aliphatic amines, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine Examples include ethanolamine, dicyclohexylamine, dicyclohexylmethylamine and the like.
Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 -5-nonene, 1,8-di Azabicyclo [5.3.0] -7-undecene, butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) and the like.
Examples of quaternary ammonium hydroxides include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, and tetra-n-hexyl ammonium hydroxide.
Examples of quaternary ammonium salts of carboxylic acids include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate, and tetra-n-butyl ammonium benzoate.
Among these, heterocyclic amines are preferable, and N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used alone or in combination of two or more.
The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3% by mass, based on the total organic solids in the photosensitive resin composition, and 0.05 to 0. More preferably, it is 0.5 mass%.

<Antioxidant>
The photosensitive resin composition of the present invention preferably contains an antioxidant.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, it is possible to prevent coloring of the cured film, or to reduce a decrease in film thickness due to decomposition, and there is an advantage of being excellent in heat-resistant transparency.
Examples of such an antioxidant include phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, A nitrate, a sulfite, a thiosulfate, a hydroxylamine derivative etc. can be mentioned. Among them, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction in film thickness, and phenolic antioxidants are the most preferable. preferable. These may be used singly or in combination of two or more.
Specific examples thereof include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated in the present specification.

  Examples of commercially available phenolic antioxidants include Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO. -50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A -613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-1 , Adeka stub 2112, Adeka stub 260, Adeka stub 522A, Adeka stub 1178, Adeka stub 1500, Adeka stub C, Adeka stub 135A, Adeka stub 3010, Adeka stub TPP, Adeka stub CDA-1, Adeka stub CDA-6, Adeka stub ZS-27, Adeka stub ZS-90, Adeka stub ZS -91 (above, product made by ADEKA), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD 1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520 L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098, Tinuvin 405 can be suitably used.

The content of the antioxidant in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass with respect to the total organic solid content of the photosensitive resin composition. Is more preferable, and 0.5 to 4% by mass is particularly preferable. By setting this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation also becomes good.
Further, as additives other than antioxidants, various ultraviolet light absorbers described in “New development of polymer additives” (Nippon Kogyo Shimbun Co., Ltd.), metal deactivators, etc. as photosensitive resin compositions May be added to

<Other ingredients>
In the photosensitive resin composition of the present invention, in addition to the above components, if necessary, an ultraviolet light absorber, a metal deactivator, an acid multiplication agent, a development accelerator, a plasticizer, a polymerization inhibitor, a thermal radical Known additives such as generators, thermal acid generators, thickeners, and organic or inorganic suspending agents can be added. Moreover, as these compounds, the description of Unexamined-Japanese-Patent No.2012-88459, Paragraph 0201-0224, Unexamined-Japanese-Patent No. 2014-238438 can also be considered, for example, and these content is integrated in this-application specification.

(Cured product and its manufacturing method)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. The cured product is preferably a cured film. Further, the cured product of the present invention is preferably a cured film obtained by the method for producing a cured product of the present invention.
The method for producing the cured product of the present invention is not particularly limited as long as it is a method for curing the photosensitive resin composition of the present invention to produce a cured product, but the following steps a to d are included in this order Is preferred.
Step a: Coating step of coating the photosensitive resin composition of the present invention on a substrate Step b: Solvent removal step of removing the solvent from the coated photosensitive resin composition Step c: Photosensitive resin composition from which the solvent has been removed Step of exposing at least a part of the object with actinic radiation step d: heat treatment step of heat treating the exposed photosensitive resin composition, and in the method of producing a cured product of the present invention, between step c and step d And the following step e is more preferable.
Step e: Development step of developing the exposed photosensitive resin composition with an aqueous developer

In the application step, the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin composition to the substrate, the substrate can be cleaned by alkaline cleaning or plasma cleaning. Furthermore, after cleaning the substrate, the substrate surface can be treated with hexamethyldisilazane or the like. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved.
Examples of the above-mentioned substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper or the like is vapor-deposited on a substrate such as those.
As the resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, poly Benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorine resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Synthetic resins such as aromatic ether resin, maleimide-olefin copolymer, cellulose, episulfide resin, etc. A substrate made of, and the like.
These substrates are rarely used as they are in the above-mentioned form, and usually, a multilayer laminate structure such as a TFT (Thin-Film Transistor) element is formed by the form of the final product.
In the case of an on-cell touch panel or the like, the photosensitive resin composition of the present invention is applied on a liquid crystal display (LCD) cell or an organic light emitting diode (OLED) cell which has been once completed as a panel. It can also be done.

  Since the photosensitive resin composition of the present invention is excellent in the corrosion resistance to metal wiring, as a substrate, one having metal wiring is preferable. The metal in the metal wiring may be titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium, oxides or alloys thereof, or laminates thereof More preferably, it is molybdenum, titanium, aluminum, copper, an alloy thereof, or a laminate thereof, and particularly preferably a laminate of copper, a copper alloy, or molybdenum / aluminum / molybdenum. The effect of the present invention can be exhibited more as it is the above-mentioned mode. The metal and the metal oxide may be used alone or in combination of two or more.

  There is no particular limitation on the method of coating on a substrate, and for example, methods such as inkjet method, slit coating method, spray method, roll coating method, spin coating method, cast coating method, slit and spin method, printing method, etc. may be used. it can.

In the solvent removal step, it is preferable to remove the solvent from the applied film by reducing pressure (vacuum) and / or heating or the like to form a dried coating on the substrate. The heating conditions of the solvent removal step are preferably about 70 to 130 ° C. and about 30 to 300 seconds. In the solvent removal step, it is not necessary to completely remove the solvent in the photosensitive resin composition, as long as at least a part of the solvent is removed.
The application step and the solvent removal step may be performed in this order, simultaneously or alternately. For example, after all the ink jet application in the application step is completed, the solvent removal step may be performed, or the substrate may be heated and the photosensitive resin composition is discharged by the ink jet application method in the application step. Solvent removal may be performed.

The exposure step is a step of generating an acid from the quinone diazide compound using an actinic ray, and developing the exposed portion irradiated with the actinic ray.
The "actinic ray" in the present invention is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating an acid from a quinone diazide compound by the irradiation, and a wide range of alpha rays, gamma rays, X It includes radiation, ultraviolet (UV) light, visible light, electron beam and the like.
In the exposure step, the obtained coating film is preferably irradiated with an actinic ray having a wavelength of 300 nm or more and 450 nm or less in a predetermined pattern.
As an exposure light source which can be used for the above-mentioned exposure process, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator etc. can be used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as h ray (405 nm) and g ray (436 nm) can be preferably used. In addition, it is also possible to adjust the irradiation light through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. The exposure dose is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, a laser exposure, and the like can be used.
It is preferable to perform the exposure in the said exposure process in the state oxygen-blocked from a viewpoint of hardening acceleration. Examples of means for blocking oxygen include exposure under a nitrogen atmosphere and exposure with an oxygen blocking film.
Further, the exposure in the exposure step may be performed on at least a part of the photosensitive resin composition from which the solvent has been removed.

After the exposure step and before the development step, post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as “PEB”) can be performed. The temperature for PEB is preferably 30 ° C. or more and 130 ° C. or less, more preferably 40 ° C. or more and 110 ° C. or less, and particularly preferably 50 ° C. or more and 100 ° C. or less.
The method of heating is not particularly limited, and known methods can be used. For example, a hot plate, an oven, an infrared heater, etc. may be mentioned.
Moreover, as heating time, in the case of a hot plate, about 1 minute-30 minutes are preferable, and about 20 minutes-120 minutes are preferable in other cases. If it is the said temperature range, the damage to a board | substrate and an apparatus can be suppressed and it can heat.

Further, the method for producing a cured product of the present invention more preferably includes, between the exposure step and the heat treatment step, a development step of developing the exposed photosensitive resin composition with an aqueous developer.
In the development step, the uncured photosensitive resin composition is removed by development using an aqueous developer to form a negative image. The developer used in the development step is preferably an alkaline aqueous developer.
The developing solution used in the developing step preferably contains a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; sodium bicarbonate and potassium bicarbonate Alkali metal bicarbonates such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, etc. Tetraalkylammonium hydroxides such as choline Alkyl) trialkyl ammonium hydroxides; silicates such as sodium silicate, sodium metasilicate; ethylamine, propylamine, diethylamine, triethyl alcohol Alkylamines such as dimethylamine; alcoholamines such as triethanolamine; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0]- Alicyclic amines such as 5-nonene can be used.
Among these, sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, choline (2-hydroxyethyl trimethyl ammonium hydroxide) are preferable.
Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as a developer.
As a preferable developing solution, the 0.4-2.5 mass% aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid deposition method (paddle method), a shower method, a dip method and the like.
A rinse process can also be performed after image development. In the rinse step, the substrate after development is washed with pure water or the like to remove the attached developer and to remove the development residue. The rinse method can use a well-known method. For example, shower rinse and dip rinse can be mentioned.
For pattern exposure and development, known methods and known developers can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

The method for producing a cured film of the present invention preferably includes a heat treatment step (post-baking) of subjecting the exposed photosensitive resin composition to a heat treatment after the exposure step, preferably after the development step. By carrying out heat treatment after developing the photosensitive resin composition of the present invention, a cured film having more excellent strength can be obtained.
The heat treatment temperature in the heat treatment step is preferably 180 ° C. or less, more preferably 150 ° C. or less, and still more preferably 130 ° C. or less. As a lower limit, 80 ° C or more is preferred, and 90 ° C or more is more preferred. The method of heating is not particularly limited, and known methods can be used. For example, a hot plate, an oven, an infrared heater, etc. may be mentioned.
Moreover, as heating time, in the case of a hot plate, about 1 minute-30 minutes are preferable, and about 20 minutes-120 minutes are preferable in other cases. If it is the said temperature range, the damage to a board | substrate and an apparatus can be suppressed and it can harden | cure.
Further, before the heat treatment step (post bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When middle baking is performed, it is preferable to perform heat treatment at a temperature of 100 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking may be divided into three or more stages and heated. The shape of the pattern can be adjusted by devising such middle baking and post baking. The heating may be performed using a known heating method such as a hot plate, an oven, or an infrared heater.

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film (insulating film) or an overcoat film (protective film), and is more suitably used as an overcoat film for a touch panel, and as an overcoat film for on-cell structure touch panel It is more preferably used. The on-cell touch panel is synonymous with the on-cell touch panel display device described later. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
The photosensitive resin composition of the present invention provides a cured film having sufficient hardness even when cured at low temperature, for example, a cured film having a hardness of H or more. The protective film formed by curing the photosensitive resin composition of the present invention is excellent in cured film physical properties, and thus is useful for applications of organic EL display devices and liquid crystal display devices.
Above all, the cured film of the present invention can be suitably used as a protective film for touch panel wiring, and can be more suitably used as a protective film for wiring in an on-cell touch panel.

  Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a cured product or resist pattern obtained by curing the photosensitive resin composition of the present invention as a structural member of a device for MEMS (Micro Electro Mechanical Systems) As a partition wall or incorporated as part of a mechanical drive component. As such a MEMS device, for example, a SAW (surface acoustic wave, surface acoustic wave) filter, a BAW (bulk wave, bulk acoustic wave) filter, a gyro sensor, a micro shutter for display, an image sensor, electronic paper, an inkjet head, Examples include parts such as biochips and sealants. More specific examples are illustrated in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010 Partition (12) and the flattening film (102) described in FIG. 4 (a) of JP-9793A, the bank layer (221) and the third interlayer insulating film (described in FIG. 10 of JP-A-2010-27591). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and described in FIG. 3 of JP-A-2010-182638. It can also be used to form a planarization film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices constant, color filters for liquid crystal display devices, protective films for color filters, on-chip color filters such as facsimiles, electronic copiers, solid-state imaging devices, etc. It can also be suitably used as a microlens of an optical system or an optical fiber connector.

(Display device and touch panel)
The display device of the present invention is characterized by having the cured film of the present invention.
Examples of the display device of the present invention include various display devices such as an organic EL display device, a liquid crystal display device, and a touch panel display device.

The organic EL display device of the present invention is characterized by having the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic compounds having various structures are used. An EL display device or a liquid crystal display device can be mentioned.
For example, as a specific example of the TFT included in the organic EL display device of the present invention, an amorphous silicon-TFT, a low temperature polysilicon-TFT, an oxide semiconductor TFT and the like can be mentioned. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a structural conceptual view of an example of the organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarization film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed in a state of covering the TFT 1. After forming a contact hole (not shown) in the insulating film 3, a wire 2 (height 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 such as a metal wiring is for connecting the TFT 1 to an organic EL element formed between the TFTs 1 or in a later step.
Furthermore, in order to planarize the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is embedded.
A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 made of ITO is formed on the planarization film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and the provision of the insulating film 8 prevents a short circuit between the first electrode 5 and a second electrode to be formed in a later step. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited and provided through a desired pattern mask, and then the entire surface of the substrate is made of Al. An active matrix type in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected with a TFT 1 for driving the same. An organic EL display device is obtained.

The liquid crystal display device of the present invention is characterized by having the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has an overcoat film (protective film) formed by using the photosensitive resin composition of the present invention, a flattening film and an interlayer insulating film, A well-known liquid crystal display device which takes a structure can be mentioned.
For example, specific examples of the TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low temperature polysilicon-TFT, oxide semiconductor TFT (for example, indium gallium zinc oxide, so-called, IGZO) and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be used for the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS (Fringe Field Switching) method, an OCB Optically Compensated Bend) and the like.
In the panel configuration, the cured film of the present invention can also be used in a liquid crystal display device of a COA (Color Filter on Array) system, and, for example, the organic insulating film (115) of JP-A-2005-284291 It can be used as the organic insulating film (212) of Japanese Unexamined Patent Publication No. 346054. Moreover, as a specific orientation system of the liquid crystal aligning film which the liquid crystal display device of this invention can take, a rubbing orientation method, an optical orientation method, etc. are mentioned. Moreover, polymer orientation support may be carried out by the PSA (Polymer Sustained Alignment) technology described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a planarizing film and an interlayer insulating film, a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens suitably provided on a color filter in a solid-state imaging device, etc. It can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix liquid crystal display device 10. As shown in FIG. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is attached. Elements of the TFT 16 corresponding to In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of liquid crystal 20 and a black matrix are arranged is provided.
The light source for the backlight is not particularly limited, and any known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red and green, fluorescent lamps (cold cathode tubes), organic EL and the like can be mentioned.
In addition, the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type (touch panel display device). Furthermore, it is possible to use a flexible type, and use as the second interlayer insulating film (48) described in JP-A-2011-145686 or the interlayer insulating film (520) described in JP-A-2009-2558758. Can.

The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or the protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. The touch panel of the present invention may be any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method. Among them, the capacitance method is preferable.
As a capacitive touch panel, those disclosed in JP 2010-28115 A and those disclosed in WO 2012/057165 can be mentioned.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7, FIG. 8 of JP-A-2012-517051), a so-called on-cell type (for example, a diagram of JP-A 2012-43394) 14, WO 2012/141148 FIG. 2 (b), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type, other configurations (for example, a diagram of Japanese Patent Application Laid-Open No. 2013-164871) 6) can be mentioned.
Moreover, FIG. 3 shows the structural-concept figure of an example of a touch-panel display apparatus.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3 and is also preferably applied to the interlayer insulating film which separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, it is preferable that they are silver, copper, aluminum, titanium, molybdenum, and these alloys.
In FIG. 3, 110 indicates a pixel substrate, 140 indicates a liquid crystal layer, 120 indicates an opposing substrate, and 130 indicates a sensor portion. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in this order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes the insulating layer (114) (also referred to as interlayer insulating film) of the pixel substrate portion, various protective films (not shown), various protective films (not shown) of the pixel substrate portion, and the opposing substrate portion Can be used as various protective films (not shown) of the above, various protective films (not shown) of a sensor part, etc.

  Furthermore, even in a static drive liquid crystal display device, it is possible to display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in Japanese Patent Application Laid-Open No. 2001-125086.

FIG. 4 is a conceptual view of another example of the touch panel display device.
A lower display panel 200 corresponding to a thin film transistor array panel including a thin film transistor (TFT) 440, and a color filter array panel including a plurality of color filters 330 on the surface facing the lower display panel 200 facing the lower display panel 200 And a liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

  The lower display panel 200 is disposed on the first insulating substrate 210, a thin film transistor (TFT) disposed on the first insulating substrate 210, an insulating film 280 formed on the top surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272. A contact hole 282 is formed in the insulating film 280 so as to expose the drain electrode 272 of the thin film transistor (TFT).

  The upper display panel 300 is disposed on one surface of the second insulating substrate 310, and the light blocking members 320 arranged in a matrix, an alignment film 350 disposed on the second insulating substrate 310, and an alignment film 350. The color filter 330 is disposed, and the common electrode 370 disposed on the color filter 330 and corresponding to the pixel electrode 290 of the lower display panel 200 applies a voltage to the liquid crystal layer 400.

  In the touch panel display device illustrated in FIG. 4, the sensing electrode 410, the insulating film 420, the driving electrode 430, and the insulating film (protective film) 280 are disposed on the other surface of the second insulating substrate 310. As described above, in the manufacture of the liquid crystal display device shown in FIG. 4, when forming the upper display panel 300, the sensing electrode 410, the insulating film 420, the driving electrode 430, etc. which are components of the touch screen are formed together. be able to. In particular, a cured film obtained by curing the photosensitive resin composition of the present invention can be suitably used for the insulating film 280 and the insulating film 420.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPMA: dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
OXE-30: methacrylic acid (3-ethyl oxetan-3-yl) methyl (Osaka Organic Chemical Industry Co., Ltd. product)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

Synthesis Example 1: Synthesis of Resin A
In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and diethylene glycol ethyl methyl ether (Toho Chemical Industry Co., Ltd.) (Hysorb EDM-S) (200 parts by mass) was charged. Subsequently, 100 parts by mass of monomers in total (25 molar equivalents of styrene, 20 molar equivalents of methacrylic acid, 45 molar equivalents of glycidyl methacrylate and 10 molar equivalents of dicyclopentanyl methacrylate) were charged and nitrogen substitution was carried out, and then stirring was gradually started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing resin A. In addition, solid content concentration of the obtained polymer solution was adjusted so that it might be 37.9 mass%.

Synthesis Examples 2 to 11: Synthesis of Resins B to K
The monomers were changed as shown in Table 1 below, and each resin B to K was synthesized in the same manner as the resin A.

  The unit of the numerical value in each monomer column described in Table 1 is mol%.

Moreover, the detail of the various components used in the Example and the comparative example other than said resin AK is shown below.
Resin L: cresol novolac resin (cresol / formaldehyde novolac resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., trade name) "EP 4020 G"
B-1: The following quinone diazide compound (NQD), TAS-200 manufactured by Toyo Gosei Kogyo Co., Ltd., esterification ratio 66%, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, NQD of α-dimethylbenzyl} phenol skeleton
B-2: TAS-250 manufactured by Toyo Gosei Co., Ltd., esterification ratio 83%, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol skeleton NQD
B-3: 4,4 '-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 Condensation products with sulfonic acid chloride (3.0 mol) B-4: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensates with chloride (2.0 mol) B-5: 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid ester (2.44) Condensate with mol)

Propylene glycol monomethyl ether acetate (PGMEA): solvent, manufactured by Daicel Co., Ltd. T-1 to T-12: the following heterocyclic compounds

  M-1 to M-5: the following maleimide compounds

Silica particle: Colloidal silica (average primary particle diameter 20 nm) dispersion liquid, solid content concentration 30.0 mass%, Nissan Chemical Industries, Ltd. PMA-ST
Adhesion promoter S-1: 3-triethoxysilylpropyl isocyanate, Shin-Etsu Chemical Co., Ltd. KBM-9007
Surfactant: Perfluoroalkyl group-containing nonionic surfactant (2% PGMEA solution), Megafac F-554 manufactured by DIC Corporation

Example 1
<Preparation of Photosensitive Resin Composition>
It was prepared as follows.
Propylene glycol monomethyl ether acetate (PGMEA): 283.8 parts Resin A: 179.2 parts (solid content 67.9 parts)
NQD: 20.0 parts Adhesion promoter S-1: 5.0 parts Maleimido compound M-1: 5.0 parts Heterocyclic compound T-2: 2.0 parts Surfactant: 5.0 Part (solid content 0.1 part)
The above components were mixed and stirred with a magnetic stirrer for 1 hour.
Then, the resultant was filtered through a membrane filter of 0.45 μm to prepare a photosensitive resin composition (solid content: 20% by mass) of Example 1.

(Examples 2 to 35 and Comparative Examples 1 to 12)
Photosensitive resin compositions of Examples 2 to 35 and Comparative Examples 1 to 12 in the same manner as Example 1 except that the components other than the surfactant were changed to the respective components and addition amounts described in Table 2. Each was prepared. In addition, solid content concentration was adjusted so that it might become 20 mass% in PGMEA which is a solvent.

-Evaluation-
<Evaluation of corrosion prevention for metal wiring>
A photosensitive resin composition is applied on a substrate obtained by sputtering the following base material I or base material II on a 4-inch silicon wafer, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. A film was formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance: 20 mW / cm ² ), and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The substrate I used was a 10 cm × 10 cm glass substrate sputtered with 10 nm of Ti and then 200 nm Cu sputtered, and the substrate II was a 10 cm × 10 cm glass substrate with 50 nm Mo and 50 nm Al. 200 nm and Mo sputtered in the order of 50 nm.
An artificial sweat of the following composition was dropped on this substrate, and after standing for one day, it was introduced into a constant temperature and humidity layer at a temperature of 85 ° C. and a humidity of 85% RH, and the time until occurrence of corrosion was evaluated based on the following criteria.
1:24 hours or less 2:24 hours or more and 78 hours or less 3:78 hours or more and 150 hours or less 4: 150 hours or more and 300 hours or less 5: 300 hours or more

-Composition of artificial sweat-
Pure water: 100.000 g
Sodium chloride: 1.000 g
・ Lactic acid: 0. 100 g
-Disodium hydrogen phosphate anhydride: 0.025 g
L-histidine hydrochloride monohydrate: 0.025 g

<Evaluation of hardness>
A photosensitive resin composition is spin-coated on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), dried in an oven at 90 ° C. for 100 seconds (prebaked), and a film having a thickness of 1.0 μm Formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance: 20 mW / cm ² ), and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The pencil hardness of this substrate was measured in accordance with JIS K5600-5-4. In addition, the pencil used the Mitsubishi Pencil Co., Ltd. product Uni, the load at the time of measurement was 750 g, the load at the time of measurement was 750 g, and the angle of the pencil was 45.
1: Less than HB 2: H
3: 2 H
4: 3 H or more

<Evaluation of Transmittance (Transparency)>
A photosensitive resin composition is slit-coated on a 1,000 mm × 1,000 mm glass substrate (trade name: XG, manufactured by Corning), dried in an oven at 90 ° C. for 100 seconds (prebaked), and a film thickness of 1. A film of 0 μm was formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance: 20 mW / cm ² ), and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The transmittance of this substrate at a wavelength of 400 nm was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) with a glass substrate (trade name: XG, manufactured by Corning) as a reference.
1: Transmittance of less than 90% 2: Transmittance of 90% or more and less than 95% 3: Transmittance of 95% or more

<Evaluation of developability>
A photosensitive resin composition was coated on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) to a film thickness of 2.0 μm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. After that, 50 μm line and space 200 mJ / cm ² exposure (illuminance 24 mW / cm ² ) was performed, and development was performed for 30 seconds at 25 ° C. using an alkaline developer (0.4% by mass aqueous solution of tetramethylammonium hydroxide). .

-Linearity evaluation-
The line edge portion of the developed substrate prepared with a 50 μm line and space was checked for linearity by an optical microscope. Evaluation criteria are shown below.
1: not dissolved in the developing solution and no pattern was formed 2: there was a rough surface in the entire line edge portion 3: almost half of the surface in the surface with a line edge 4: line edge There is almost no clatter in the department

-Undercut evaluation-
The developed substrate produced with a 50 μm line and space was observed by scanning electron microscopy (SEM) to determine how undercuts, which are grooves or depressions, occur on the side surface of the line pattern at the interface between the substrate and the pattern.
1: Do not dissolve in developer and can not form a pattern 2: Undercut is included 3: No undercut is included

  The evaluation results are summarized in Table 3.

  1: TFT (thin film transistor) 2: wiring 3: insulating film 4: planarizing film 5: first electrode 6: glass substrate 7: contact hole 8: insulating film 10: liquid crystal display device 12 A backlight unit 14, 15: glass substrate, 16: TFT, 17: cured film, 18: contact hole, 19: ITO transparent electrode, 20: liquid crystal, 22: color filter, 110: pixel substrate, 111: polarizing plate , 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: opposing substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: retardation Film 125: detection electrode for sensor 126: adhesive layer 127: polarizing plate 130: sensor unit 140: liquid crystal layer 200: lower display panel 210: first insulating substrate 20: gate electrode, 240: gate insulating film, 250: semiconductor layer, 260, 262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: pixel electrode, 300 Upper panel 310, second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: drive Electrode, 440: TFT

Claims (14)

A polymer component satisfying at least one of the following I and II:
A quinone diazide compound,
Solvent,
At least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds,
A photosensitive resin composition comprising a maleimide compound.
I: Polymer component including a structural unit having a carboxy group and / or a salt thereof and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof And a polymer component including a polymer having a structural unit having an epoxy group and / or an oxetanyl group The photosensitive resin composition of Claim 1 whose said heterocyclic compound is a compound represented by either of following formula D1-formula D12.

In formulas D1 to D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group. , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4. The photosensitive resin composition of Claim 1 or 2 in which the said maleimide compound contains the compound represented by following formula E1.

In formula E1, R ^e1 each independently represents a single bond, an alkylene group, -SO _2- , -SO-, -S- or -O-, and R ^e2 each independently represents a halogen atom or an alkyl group. And m1 represent an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.   The photosensitive resin composition according to any one of claims 1 to 3, further comprising silica particles.   The photosensitive resin composition of Claim 4 whose average primary particle diameter of the said silica particle is 1-50 nm.   The photosensitive resin composition of Claim 4 or 5 whose content of the said silica particle is 5 mass% or more and less than 40 mass% with respect to the total solid of the photosensitive resin composition.   The photosensitive resin composition according to claim 2, wherein the heterocyclic compound is a compound represented by any one of Formula D1, Formula D2 and Formula D4 to Formula D12.   The photosensitive resin composition of Claim 7 whose said heterocyclic compound is a compound represented by either of said Formula D4-Formula D12. A method for producing a cured product, comprising at least steps a to d in this order.
Step a: Coating step of coating the photosensitive resin composition according to any one of claims 1 to 8 on a substrate Step b: Solvent removal step of removing a solvent from the coated photosensitive resin composition Step c : Exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed by actinic rays Step d: Heat treatment step of subjecting the exposed photosensitive resin composition to heat treatment The manufacturing method of the hardened | cured material of Claim 9 which includes the process e between the process c and the process d.
Step e: Development step of developing the exposed photosensitive resin composition with an aqueous developer   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8.   The cured film according to claim 11, which is an interlayer insulating film or an overcoat film.   The display apparatus which has a cured film of Claim 11 or 12.   A touch panel comprising the cured film according to claim 11 or 12.

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